Molded product comprising polarized olefin-based polymer and property thereof

ABSTRACT

The object of the invention is to provide a novel olefin-based molded product useful for various applications. 
     An olefin-based molded product comprising a polymer including a structural unit of at least one polar olefin monomer represented by the general formula (I) CH2=CH—R 2 —Z(R 1 )n is provided. In the formula, Z is a hetero atom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium; R 1  is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms; n is an integer of 1 or 2 depending on the atomic species of Z; and R 2  is a substituted or unsubstituted hydrocarbylene group having 2 to 20 carbon atoms.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of U.S. patent applicationSer. No. 16/979,984, filed on Sep. 11, 2020, which claims priority under37 U.S.C. § 371 to International Patent Application No.PCT/JP2019/010592, filed Mar. 14, 2019, which claims priority to and thebenefit of Japanese Patent Application No. 2018-046829, filed on Mar.14, 2018. The contents of these applications are hereby incorporated byreference in their entireties.

TECHNICAL FIELD

The present invention relates to an olefin-based molded productcomprising a polar olefin-based polymer. More particularly, the presentinvention relates to an olefin-based molded product, which comprises apolar olefin-based polymer having properties such as a self-healingability, and is useful for various applications.

BACKGROUND ART

Conventionally, olefin-based molded products such as a polyolefin filmhave been used in various ways as packaging materials, etc., howeverutilization as a high-performance molded article imparted with a specialfunction (such as self-healing ability, and shape-memory property) hasbeen limited to some applications.

By developing a high-performance self-healing material, not only wasteis reduced and sustainability is acquired, but also products superior insafety and reliability can be created (Non Patent Literature 1). Aself-healing material is particularly attractive in applications where adamage is hardly detected, or in applications where repair is costly orimpossible (such as a medical implant in a human body, a submarinepipeline, and a device in outer space). Wool has constructed a unifiedtheory based on the De Gennes' reptation dynamics and the entanglementpercolation model. Following this unified theory, by jointing twofractures of an amorphous polymer through five steps (surfacerearrangement, approach of the polymer chains, wetting, diffusion, andchain randomization), re-repair can be achieved at a temperature higherthan the glass transition temperature (Tg) of the amorphous polymer.However, due to the slow rate of the last two steps, in the case of ahigh molecular weight polymer, the healing time for jointing thefractures becomes long. Therefore, in most cases, an efficientdiffusion-dependent repair occurs at a high temperature (120° C. orhigher) (Non Patent Literature 1). Several carefully designed materialswith an extrinsic self-healing ability based on a covalent bond havebeen reported. However, most of these strategies require an input of acatalyst/monomer, or external energy. Several clear dynamicsupramolecular approaches (metal-ligand interaction, multivalenthydrogen bonds, etc.) toward a material with an intrinsic autonomousself-healing have been established (Non Patent Literature 2). However,to date, improvement has been limited to a soft elastomer, and theimprovement realized so far includes an elaborately designed complexmacromolecule structure.

Most recently, Aida, et al. reported an amorphous polymer including aseries of hydrogen bonds that exhibited facile repairability, and robustmechanical properties under a specific pressure (Non Patent Literature3). As described above, it has been a difficult task to develop amaterial having both an autonomous self-healing function and strongmechanical properties.

PRIOR ART DOCUMENTS Non Patent Literature

-   [Non Patent Literature 1] B. J. Blaiszik, S. L. B. Kramer, S. C.    Olugebefola, J. S. Moore, N. R. Sottos, and S. R. White,    “Self-healing polymers and composites”, Annu. Rev. Mater. Res., 40,    179-211 (2010).-   [Non Patent Literature 2] S. Kim, “Superior Toughness and Fast    Self-Healing at Room Temperature Engineered by Transparent    Elastomers”, Adv. Mater. 30, 1705145 (2018).-   [Non Patent Literature 3] Y. Yanagisawa, Y. Nan, K. Okuro, and T.    Aida, “Mechanically Robust, Readily Repairable Polymers via Tailored    Noncovalent Cross-Linking”, Science 359, 72-76 (2018) DOI:    10.1126/science.aam7588.

SUMMARY OF THE INVENTION Technical Problem

The present invention has been made under such circumstances with anobject to provide a novel olefin-based molded product useful for variousapplications.

Solution to Problem

The present inventors have deliberately conducted studies to attain theabove object. The present inventors have found that a polar olefin-basedpolymer obtained by polymerizing a polar olefin monomer using arare-earth metal complex can be utilized as a raw material for a moldedproduct such as a film, and that a molded product such as a filmproduced by using the polymer has various functionalities such as anautonomous self-healing ability, or a shape-memory property. The presentinvention has been completed based on these findings.

That is, the essentials of the present invention are as follows.

[1] An olefin-based molded product comprising a polymer including astructural unit of at least one polar olefin monomer represented by thegeneral formula (I):

CH₂=CH—R²—Z(R¹)_(n)  (I)

wherein, Z is a hetero atom selected from the group consisting ofnitrogen, oxygen, phosphorus, sulfur, and selenium; R¹ is a substitutedor unsubstituted hydrocarbyl group having 1 to 30 carbon atoms; n is aninteger of 1 or 2 depending on the atomic species of Z; and R² is asubstituted or unsubstituted hydrocarbylene group having 2 to 20 carbonatoms.[2] The olefin-based molded product according to [1] above, wherein thepolymer is a copolymer including an additional structural unit of atleast one nonpolar olefin monomer.[3] The olefin-based molded product according to [2] above, wherein thecopolymer includes an alternating sequence of the structural unit of atleast one polar olefin monomer represented by the general formula (I)and the structural unit of at least one nonpolar olefin monomer, and apolymerization sequence of the structural unit of at least one nonpolarolefin monomer. An embodiment of the olefin-based molded product of [3]above comprising said copolymer shows an X-ray diffraction peak derivedfrom crystalline nanodomains formed by aggregation of the polymerizationsequences.[4] The olefin-based molded product according to any one of [1] to [3]above, wherein the polar olefin monomer is a polar olefin monomerrepresented by the general formula (II).

In the formula, Z is a hetero atom selected from the group consisting ofnitrogen, oxygen, phosphorus, sulfur, and selenium; R′ is a substitutedor unsubstituted hydrocarbyl group having 1 to 30 carbon atoms; n is aninteger of 1 or 2 depending on the atomic species of Z; R³ is ahydrocarbylene group having 1 to 5 carbon atoms; R⁴ is a halogen atom, ahydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms, and when R⁴ is ahydrocarbyl group, the hydrocarbyl groups may bond together to form acondensed ring; and m is an integer of 0 to 4.

[5] The olefin-based molded product according to any one of [1] to [4]above, wherein the proportion of the structural unit of polar olefinmonomer in the total structural units in the polymer is 20 mol % ormore.

[6] The olefin-based molded product according to any one of [1] to [5]above, wherein the number average molecular weight of the polymer is2.0×10³ or more.[7] The olefin-based molded product according to any one of [2] to [6]above, wherein the polymer is a copolymer including at least structuralunits respectively represented by the following formulas (III) and (IV).

In the formula, R¹ , R³, R⁴, Z, m and n respectively have the samemeanings as in the formula (II), and each of x and y stands for theproportion (molar ratio) of a structural unit in the total sequences ofthe copolymer, and is a positive number that satisfies x>0, y >0, x>y,and 80%<x+y<100%).

[⁸] An olefin-based molded product comprising a polymer including astructural unit of a polar olefin monomer, and having a toughness valueof 0.5 MJm⁻³ or more.

In this regard, examples of a polar group contained in the polar olefinmonomer include —Z(R¹)_(n), in the formula (I). The same applies to [9]and [10] below. Examples of a polymer used in a molded product of thisembodiment include the (co)polymer according to [1] to [7] above. Amongothers, the copolymer according to [7] above is preferable. The moldedproduct preferably exhibits a toughness value in the above range at theservice temperature of the molded product (for example, 25° C., when itis room temperature). Further, the molded product preferably has atensile strength of 0.5 MPa or more, and/or an elongation at break ofmore than 100%. [⁹] An olefin-based molded product comprising a polymerincluding a structural unit of a polar olefin monomer, and having atensile strength of 0.5 MPa or more.

Examples of a polymer used in a molded product of this embodimentinclude the (co)polymers according to [1] to [7] above. Among others,the copolymer according to [7] is preferable. The molded productpreferably exhibits a tensile strength in the above range at the servicetemperature of the molded product (for example, 25° C., when it is roomtemperature). Further, the molded product preferably has a tensilestrength in the above range, and also an elongation at break of morethan 100%, and/or a toughness value of 0.5 MJm⁻³ or more.

An olefin-based molded product comprising a polymer including astructural unit of a polar olefin monomer, and having an elongation atbreak of more than 100%.

Examples of a polymer used in a molded product of this embodimentinclude the (co)polymers according to [1] to [7] above. Among others,the copolymer according to [7] is preferable. The molded productpreferably exhibits an elongation at break in the above range at theservice temperature of the molded product (for example, 25° C., when itis room temperature). Further, the molded product preferably has anelongation at break in the above range, and also a toughness value of0.5 MJm⁻³ or more, and/or a tensile strength of 0.5 MPa or more.

The olefin-based molded product according to any one of [1] to [10]above, which is a film.

The olefin-based molded product according to any one of [1] to [11]above, which is used as a self-healing material. One embodiment of thepresent invention is a self-healing material which is constituted withthe olefin-based molded product according to any one of [1] to [11]above, or which includes the olefin-based molded product. Anotherembodiment thereof is a self-healing molded product which is constitutedwith the olefin-based molded product according to any one of [1] to [11]above, or which includes the olefin-based molded product.

One embodiment of the self-healing molded product comprises the polymerexhibiting a glass transition point below room temperature (25° C.).

One embodiment of the self-healing molded product exhibits aself-healing rate of 80% or more within 5 days.

The olefin-based molded product according to any one of [1] to [11]above, which is used as a shape-memory material. One embodiment of thepresent invention is a shape-memory material which is constituted withthe olefin-based molded product according to any one of [1] to [11]above, or which includes the olefin-based molded product. Anotherembodiment thereof is a shape-memory molded product which is constitutedwith the olefin-based molded product according to any one of [1] to [11]above, or which includes the olefin-based molded product.

One embodiment of the shape-memory molded product comprises the polymerexhibiting a glass transition point of about room temperature (e.g., 15°C. to 35° C.), or above room temperature. For example, the shape-memorymolded product has a nature that it maintains a constant shape S1 at atemperature Tu at which it is used (for example, room temperature), itis deformed at a temperature Td which exceeds Tg (Tu<Tg) (and is belowthe melting point if there is a melting point), and then cooled down tothe service temperature Tu so as to maintain the shape S2, and furtherit can be returned to the original shape S1 at a temperature Tf which isbeyond Tg (and is below the melting point if there is a melting point)(Tf may be the same as or different from Td).

One embodiment of the shape-memory molded product exhibits a shape fixedrate and a shape recovery rate of 80% or more.

The polymer according to any one of [1] to [7] above.

A coating composition comprising at least one of the polymers accordingto any one of [1] to [7] above.

The composition may include a liquid or solid medium together with thepolymer. The polymer may be dissolved or not dissolved (for example,dispersed) in the medium.

Advantageous Effects of the Invention

According to the present invention, a novel olefin-based molded productuseful for various applications may be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the structures of metallocene complexes usedin Examples.

FIG. 2 is a diagram showing the structures of polar olefin monomers usedin Examples.

FIG. 3 is a diagram showing the analysis values and a ¹ H NMR spectrumof the polymer P2 obtained in Run 3 of Table 1.

FIG. 4 is a diagram showing a ¹³C NMR spectrum of the polymer P2obtained in Run 3 of Table 1.

FIG. 5 is a diagram showing the analysis values and a partial enlargedview of ¹³C NMR spectrum of the polymer P2 obtained in Run 3 of Table 1.

FIG. 6 is a diagram showing a DSC curve of the polymer P2 obtained inRun 3 of Table 1.

FIG. 7 is a diagram showing a transmission spectrum of a 0.5 mm-thickfilm sample of the copolymer P2. A diagram (photo) of the film placed ona logo is shown inside.

FIG. 8 is diagrams showing the mechanical properties concerning thecopolymers P1 to P5. A of FIG. 8 shows stress-strain curves at a testingrate of 200 mm·min⁻¹. B of FIG. 8 shows tensile strength/hysteresiscurves of the copolymer P5. Ten cycles of 1000% elongation wereperformed. The photo (top) after ten cycles of 1000% elongation andhealing, and the photo (bottom) of the original state are also shown inthe diagram. C of FIG. 8 is a tensile strength/hysteresis curve (firstcycle) of the original sample of the copolymer P5 and the sample after1000% elongation and 3-hour relaxation.

FIG. 9 is a diagram showing the analysis values and a ¹H NMR spectrum ofthe polymer P6 obtained in Run 5 of Table 3.

FIG. 10 is a diagram showing a ¹³C NMR spectrum of the polymer P6obtained in Run 5 of Table 3.

FIG. 11 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer P6 obtained in Run 5 of Table3.

FIG. 12 is a diagram showing a DSC curve of the polymer P6 obtained inRun 5 of Table 3.

FIG. 13 is a diagram showing the analysis values and a ¹H NMR spectrumof the polymer P7 obtained in Run 7 of Table 3.

FIG. 14 is a diagram showing a ¹³C NMR spectrum of the polymer P7obtained in Run 7 of Table 3.

FIG. 15 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer P7 obtained in Run 7 of Table3.

FIG. 16 is a diagram showing a DSC curve of the polymer P7 obtained inRun 7 of Table 3.

FIG. 17 is a diagram showing the analysis values and a ¹H NMR spectrumof the polymer obtained in Run 9 of Table 3.

FIG. 18 is a diagram showing a ¹³C NMR spectrum of the polymer obtainedin Run 9 of Table 3.

FIG. 19 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer obtained in Run 9 of Table 3.

FIG. 20 is a diagram showing a DSC curve of the polymer obtained in Run9 of Table 3.

FIG. 21 is a diagram showing the analysis values and a¹I-INMR spectrumof the polymer P8 obtained in Run 11 of Table 3.

FIG. 22 is a diagram showing a ¹³C NMR spectrum of the polymer P8obtained in Run 11 of Table 3.

FIG. 23 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer P8 obtained in Run 11 of Table3.

FIG. 24 is a diagram showing a DSC curve of the polymer P8 obtained inRun 11 of Table 3.

FIG. 25 is a diagram showing the analysis values and a¹I-INMR spectrumof the polymer P9 obtained in Run 13 of Table 3.

FIG. 26 is a diagram showing a ¹³C NMR spectrum of the polymer P9obtained in Run 13 of Table 3.

FIG. 27 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer P9 obtained in Run 13 of Table3.

FIG. 28 is a diagram showing a DSC curve of the polymer P9 obtained inRun 13 of Table 3.

FIG. 29 is a diagram showing the analysis values and a¹I-1 NMR spectrumof the polymer P10 obtained in Run 15 of Table 3.

FIG. 30 is a diagram showing a ¹³C NMR spectrum of the polymer P10obtained in Run 15 of Table 3.

FIG. 31 is a diagram showing the analysis values and a partial enlargedview of a ¹³C NMR spectrum of the polymer P10 obtained in Run 15 ofTable 3.

FIG. 32 is a diagram showing a DSC curve of the polymer P10 obtained inRun 15 of Table 3.

FIG. 33 is diagrams showing the mechanical properties concerning thecopolymers P6 to P10. A of FIG. 33 is stress-strain curves of thecopolymers P6 to P10 at a testing rate of 200 mm·min⁻¹. B of FIG. 33 istensile strength/hysteresis curves of the copolymer P6. Ten cycles of1000% elongation were performed. C of FIG. 33 is tensilestrength/hysteresis curves of the copolymer P7. D of FIG. 33 is tensilestrength/hysteresis curves of the copolymer of Run 9 in Table 3. E ofFIG. 33 is tensile strength/hysteresis curves of the copolymer P8.

FIG. 34 is diagrams showing the self-healing ability of an alternatingAP-E copolymer film. A of FIG. 34 is optical images (photos) of a filmsample of the copolymer P2 in a fractured state (bottom), and in astretched state (top) after healing at 25° C. for 5 min. A fracturedsample was prepared by completely cutting a film into two separatepieces using a razor blade. A healed sample was prepared by jointing thecut surfaces together, lightly pressing them for 15 sec, and thenallowing them to heal in air at 25° C. for 5 min. B of FIG. 34 isstress-strain curves showing the test results of self-healing ability ofthe copolymer P2 in air at 25° C. C of FIG. 34 is stress-strain curvesshowing the test results of self-healing ability of the copolymer P5 inair at 25° C. D of FIG. 34 is optical microscope observation images(photos) of a sample of the copolymer P5 damaged in air at 25° C. (left)and then healed (right). The film of the copolymer P5 was nicked with arazor blade and allowed to recover in air for 5 min. E of FIG. 34isoptical microscope observation images (photos) of a sample of thecopolymer P2 damaged in water at 25° C. (left) and then healed (right).The film of the copolymer P2 was nicked with a razor blade and allowedto recover in water for 5 min. F of FIG. 34 is stress-strain curvesshowing the test results of the self-healing ability of the copolymer P2in water at 25° C. G of FIG. 34 is stress-strain curves showing the testresults of the self-healing ability of the copolymer P2 in water at 37°C. H of FIG. 34 is stress-strain curves showing comparative test resultsof the self-healing ability of the copolymer P2 (ii) in water, (iii) in1 M-HCl, and (iv) in 1 M-NaOH at 25° C., for 36 hours. I of FIG. 34 isstress-strain curves showing the test results of the self-healingability of the copolymer P6 in air at 25° C. J of FIG. 34 isstress-strain curves showing the test results of the self-healingability of the copolymer P7 in air at 25° C. K of FIG. 34 isstress-strain curves showing the test results of the self-healingability of the copolymer P8 in air at 25° C. L of FIG. 34 isstress-strain curves showing the test results of the self-healingability of the copolymer of Run 9 in Table 3 in air at 25° C.

FIG. 35 is diagrams (photos) showing the shape-memory property of thecopolymer P10. The left one is the original shape of a molded sample ofthe copolymer P10. The middle one shows a sample of the molded copolymerP10 stretched in a water bath at 80° C. The shape of the P10 sample wasfixed by releasing the force at room temperature. The right one shows asample of the molded copolymer P10 whose original shape was recovered ina water bath at 80° C. for 2 min.

FIG. 36 is diagrams showing a state of a predetermined polymer containedin an example of a molded product of the present invention. A is a TEMimage (photo). B is a schematic diagram, in which the curves representalternating sequence chains —(A)—alt —(B)— of a polar olefinic monomer(A) such as anisylpropylene, and a nonpolar olefinic monomer (B) such asethylene; and the circles represent crystalline nano domains formed byaggregation of homopolymerization sequences —(B)—(B)— of a nonpolarolefinic monomer (B) such as ethylene.

FIG. 37 shows the WAXD measurement results of a film of the polymer P5produced in Example.

FIG. 38 shows the SAXS measurement result of a film of the polymer P5produced in Example.

FIG. 39 is diagrams (photos) showing the shape-memory property of a filmsample of the copolymer P9 produced in Example. “a” of FIG. 39 shows theoriginal shape of a molded sample of the copolymer P9. “b” of FIG. 39shows a deformed sample of the molded copolymer P9 stretched at 50° C.“c” of FIG. 39 shows a state in which the sample of b maintains thedeformed shape at 20° C. “d” of FIG. 39 shows the sample of the moldedcopolymer P9 which original shape was recovered in a water bath at 50°C. for 5 sec.

FIG. 40 is a graph showing a dual shape-memory cycle at 50° C. of a filmsample of the copolymer P9 produced in Example.

DESCRIPTION OF THE EMBODIMENTS

The present invention will be described in detail below.

The present inventors have found a new kind of olefin-based materialthat can be obtained by one-step polymerization of a polar olefinmonomer represented by a predetermined formula (such as anisylpropyleneor its derivative) using a scandium complex. This novel material isuseful as a raw material for a molded product (such as a film). Inparticular, in the case of a copolymer with a nonpolar olefin monomer(such as ethylene), it has mainly an alternating sequence of a nonpolarolefin monomer (such as ethylene)—a polar olefinic monomer (such asanisylpropylene or its derivative), the material can exhibit a widerange of glass transition temperature, and a variety of mechanicalproperties (rigid plastic, flexible plastic, elastomer, or stresssoftening material) by regulating one or more of the polymerizationratio of each monomer, molecular weight, monomer type, etc. Anembodiment of the material is an elastomer and a self-healing material.Specifically, among the above materials, an elastomer exhibits excellentelasticity, and elastic recovery, and in the case of an autonomousself-healing elastomer, high tensile strength and toughness. Anautonomous self-healing elastomer is capable of self-healing not only inair but also in water, and an acid or alkaline solution without the needfor external energy or stimulation. Even more surprisingly, the healedmaterial exhibits excellent tensile strength and elongation, andexhibits higher values compared to any heretofore reported self-healingmaterial after self-healing, or self-healing material beforeself-healing.

Another embodiment of the material is rigid plastic, which showedremarkable shape-memory property.

The present invention relates to an olefin-based molded productcomprising a polymer including a structural unit of at least one polarolefin monomer represented by the general formula (I):

CH₂═CH—R²—Z(R¹)—  (I)

In the formula, Z is a hetero atom selected from the group consisting ofnitrogen, oxygen, phosphorus, sulfur, and selenium; R¹ is a substitutedor unsubstituted hydrocarbyl group having 1 to 30 carbon atoms; n is aninteger of 1 or 2 depending on the atomic species of Z; and R² is asubstituted or unsubstituted hydrocarbylene group having 2 to 20 carbonatoms.

<Method for Producing Polar Olefin-Based Polymer>

A method for producing a polymer including a structural unit of at leastone polar olefin monomer represented by the general formula (I), namelya polymer of at least one polar olefin monomer represented by thegeneral formula (I) (hereinafter also referred to as “polar olefin-basedpolymer”) to be contained in an olefin-based molded product of thepresent invention will be described below. A mere expression of“polymer” is meant herein to include a homopolymer and a copolymerunless otherwise specified.

(Catalyst Composition)

The polar olefin-based polymer may be obtained, for example, bypolymerizing at least one kind of polar olefin monomer represented bythe general formula (I) using a catalyst composition containing ametallocene complex and an ionic compound. It may be copolymerized witha monomer other than the polar olefin monomer represented by the generalformula (I), and particularly a polar olefin-based polymer copolymerizedwith at least one nonpolar olefin monomer is preferable.

(Metallocene Complex)

There is no particular limitation on the metallocene complex, andexamples thereof include the scandium complex(C₅Me₄SiMe₃)Sc(CH₂Cl₆H₄NMe₂-o)₂ described in Examples.

A metallocene complex can be synthesized by the method described above,for example, the method according to (1) X. Li, M. Nishiura, K. Mori, T.Mashiko, and Z. Hou, Chem. Commun. 4137-4139 (2007), (2) M. Nishiura, J.Baldamus, T. Shima, K. Mori, and Z. Hou, Chem. Eur. J., 17, 5033-5044(2011), (3) F. Guo, M. Nishiura, H. Koshino, and Z. Hou, Macromolecules,44, 6335-6344 (2011), (4) Reference: Tardif O., Nishiura M., and HouZ.M., Organometallics, 22, 1171, (2003), (5) Reference: Hultzsch K.C.,Spaniol T.P., and Okuda J., Angew. Chem. Int. Ed, 38, 227, (1999), (6)Reference: International Publication No. WO2006/004068, (7) Reference:Japanese Patent Laid-Open No. 2008-222780, or (8) Reference: JapanesePatent Laid-Open No. 2008-095008.

(Ionic Compound)

When the ionic compound is combined with the metallocene complex, themetallocene complex develops an activity as a polymerization catalyst.As the mechanism, it is considered that an ionic compound reacts with ametallocene complex to form a cationic complex (active species).

There is no particular limitation on the ionic compound to be containedin the catalyst composition, and examples thereof include a combinationof those selected respectively from non-coordinating anions and cations.

Preferable examples thereof include triphenylcarboniumtetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate. The ionic compounds may be usedsingly or in combination of two or more kinds thereof.

Among these ionic compounds, particularly preferable examples includetriphenylcarbonium tetrakis(pentafluorophenyl)borate.

In the catalyst composition, the molar ratio of an ionic compound withrespect to a metallocene complex varies depending on the kinds of thecomplex and the ionic compound, and may be set appropriately.

For example, when the ionic compound is composed of a carbonium cationand a boron anion (e.g., [Ph₃C][B(C₆F₅)₄]), the molar ratio ispreferably from 0.5 to 1 with respect to the central metal of ametallocene complex. When it is an alkylaluminum compound such asmethylaluminoxane, the molar ratio is preferably about 10 to 4000 withrespect to the central metal of a metallocene complex.

It is believable that the ionic compound ionizes a metallocene complex,namely cationizes it to a catalytically active species. When the ratiois within the above range, the metallocene complex can be sufficientlyactivated, while the ionic compound composed of a carbonium cation and aboron anion does not become excessive, so that the risk of causing anundesired reaction with a monomer to be polymerized can be reduced.

(Method for Producing Polymer)

Using the catalyst composition as a polymerization catalyst composition,an olefin-based polymer can be produced by polymerizing (additionpolymerization) a polar olefin monomer, and preferably by polymerizing(addition polymerization) a nonpolar olefin monomer and a polar olefinmonomer.

When 1) a composition containing each constituent (such as metallocenecomplex, or ionic compound) is supplied into a polymerization reactionsystem, or 2) each constituent is supplied separately into apolymerization reaction system to form a composition in the reactionsystem, which may be used as a polymerization catalyst composition.

In 1) above, the expression “a composition is supplied” includes that ametallocene complex (active species) activated by a reaction with anionic compound is supplied.

Specifically, the method for producing a polymer may be performed, forexample, by the following procedure.

1. A polymerizable monomer is supplied into a system (preferably aliquid phase) containing a catalyst composition to be used in the methodfor producing a polymer, and polymerized. By doing so, when the monomeris a liquid, it may be supplied by dropping, and when it is a gas, itmay be supplied through a gas tube (such as bubbling in the case of aliquid phase reaction system).

2. A catalyst composition to be used in the method for producing apolymer is added to a system (preferably in a liquid phase) comprising apolymerizable monomer, or constituents of a catalyst composition areadded individually to cause polymerization. The added catalystcomposition may be prepared in advance (preferably prepared in theliquid phase), and then activated (in this case, it is preferable to addthe same without exposure to air).

Further, the production method may be any method, such as a gas phasepolymerization method, a solution polymerization method, a suspensionpolymerization method, a liquid phase bulk polymerization method, anemulsion polymerization method, and a solid phase polymerization method.In the case of a solution polymerization method, there is no particularlimitation on the solvent used, insofar as it is a solvent which isinert in the polymerization reaction, able to dissolve the monomer andthe catalyst, and does not interact with the catalyst. Examples thereofinclude a saturated aliphatic hydrocarbon, such as butane, pentane,hexane, and heptane; a saturated alicyclic hydrocarbon, such ascyclopentane, and cyclohexane; an aromatic hydrocarbon, such as benzeneand toluene; and a halogenated hydrocarbon, such as methylene chloride,chlorobenzene, bromobenzene, and chlorotoluene.

Also, a solvent that is not toxic to living body is preferable.Specifically, an aromatic hydrocarbon, especially toluene, is preferred.The solvents may be used singly, or a mixed solvent combining two ormore kinds thereof may be used.

The amount of the solvent used is arbitrary, but for example, the amountcorresponding to the concentration of a complex contained in thepolymerization catalyst of 1.0×10⁻⁵ to 1.0×10⁻¹ mol/L is preferable.

The amount of the monomer to be supplied to the polymerization reactionmay be appropriately set according to the desired polymer to beproduced, and, for example, the monomer is preferably 100 times or more,200 times or more, or 500 times or more as much as the metallocenecomplex constituting the polymerization catalyst composition in terms ofmolar ratio.

When the polymerization is carried out by solution polymerization, anypolymerization temperature, for example, in a range of −90 to 100° C.may be used. It may be appropriately selected depending on the kind ofmonomer to be polymerized, but usually it may be around roomtemperature, namely about 25° C.

The polymerization time is about several sec to several days, and it maybe appropriately selected depending on the kind of monomer to bepolymerized. It may be 1 hour or less, and in some cases even 1 min orless.

However, these reaction conditions may be appropriately selecteddepending on the polymerization reaction temperature, the type and molaramount of the monomer, the kind and amount of the catalyst composition,or the like, and not limited to the range indicated above.

In an embodiment in which the polymer is produced as a copolymer,

-   1) a random copolymer or an alternating copolymer can be produced by    polymerizing a mixture of two or more kinds of monomers in the    presence of a catalyst composition, or-   2) a block copolymer can be produced by sequentially supplying each    monomer into the reaction system containing a catalyst composition.

After the polymerization step, it is possible to perform an optionalstep, such as a purification step, or a step of deriving a polar groupsuch as a step of eliminating R1 in a polar group.

(Polar olefin monomer)

A polar olefin monomer used in the method for producing a polymer is apolar olefin monomer including a polar group. A polar olefin monomerrepresented by the following general formula (I) is preferable.

CH₂═CH—R²—Z(R¹)_(n)  (I)

In general formula (I), Z is a hetero atom selected from the groupconsisting of nitrogen, oxygen, phosphorus, sulfur, and selenium; R¹ isa substituted or unsubstituted hydrocarbyl group having 1 to 30 carbonatoms; and n is an integer of 1 or 2 depending on the atomic species ofZ.

In the method for producing a polymer, it is considered that a heteroatom in a polar olefin monomer interacts with the central metal of acatalyst to form an intramolecular chelate, which promotes theinteraction between the catalyst and the olefin unit, promotes thepolymerization activity of the polar olefin monomer, and exhibits uniquestereoselectivity.

There is no particular limitation on R¹ in the general formula (I),insofar as an intramolecular interaction among a hetero atom in thepolar group of a polar olefin monomer, the olefin unit, and the centralmetal of a catalyst is formed in the polymerization reaction. R¹ isusually a substituted or unsubstituted hydrocarbyl group having 1 to 30carbon atoms; and preferably a linear, branched, or cyclic alkyl group,a linear, or branched alkenyl group, or a linear, or branched alkynylgroup having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6carbon atoms; an alkyl group, an alkenyl groups, a cyclic alkyl groupsubstituted with an alkynyl group having 1 to 10 carbon atoms (whereinthe number of alkyl groups, alkenyl groups, or alkynyl groups as asubstituent, and the substitution position in the cyclic alkyl group arenot particularly limited); an aryl group; or an aryl group substitutedwith an alkyl group, an alkenyl group, or an alkynyl group having 1 to10 carbon atoms (wherein the number of alkyl groups, alkenyl groups, oralkynyl groups as a substituent, and the substitution position in thearyl group are not particularly limited). In this case, the cyclic alkylgroup or the aryl group may form a saturated or unsaturated condensedring.

The hydrocarbyl group in the substituted hydrocarbyl group is the sameas the hydrocarbyl group described above. A substituted hydrocarbylgroup means a hydrocarbyl group in which at least one hydrogen atom issubstituted with a halogen atom, or the like.

R² acts as a spacer connecting the polar group and the olefin moiety inthe polar olefin monomer. There is no particular limitation on R²,insofar as an intramolecular interaction among a hetero atom in thepolar group of a polar olefin monomer, the olefin unit, and the centralmetal of a catalyst is formed in the polymerization reaction. R²preferably has 2 to 20 carbon atoms from the viewpoint of forming theintramolecular interaction. As the number of carbon atoms of R², thenumber of carbon atoms suitable for forming an intramolecularinteraction among a hetero atom, the olefin unit, and the central metalof a catalyst in the polymerization reaction may be selected using thepolymerization activity, or the like as the index depending on the kindof a hetero atom represented by Z, the kind of a substituent representedby R′, etc. Usually, R² is a hydrocarbylene group having 2 to 11 carbonatoms. It is more preferably a linear or branched alkylene group having2 to 3 carbon atoms; a cyclic alkylene group having 3 to 11 carbonatoms; an arylene group having 6 to 11 carbon atoms; or an aralkylenegroup having 7 to 11 carbon atoms. Examples of the substituent of R²include a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms,an alkylthio group having 1 to 10 carbon atoms, an alkylamino grouphaving 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbonatoms.

One embodiment of the compound represented by the general formula (I) isa compound represented by the general formula (II).

Z, R¹ , and n in the general formula (II) are synonymous with thedefinitions described in connection with the general formula (I). Z inthe general formula (II) is preferably oxygen. R¹ in the general formula(II) is preferably a linear, branched, or cyclic alkyl group having 1 to3 carbon atoms.

The bonding position of —Z(R¹)_(n) in the aromatic ring is notparticularly limited, but it is preferably the o-position.

Usually, R³ is a hydrocarbylene group having 1 to 5 carbon atoms. Morepreferably, it is a linear or branched alkylene group having 1 to 3carbon atoms; or a cyclic alkylene group having 3 to 5 carbon atoms.

R⁴, which is a substituent of the aromatic ring, is a halogen atom, ahydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms,or an alkoxy group having 1 to 10 carbon atoms. When R⁴ is a hydrocarbylgroup, the groups may bond together to form a saturated, unsaturated, orhetero condensed ring. Although there is no particular limitation on thesubstitution position of R⁴ in the aromatic ring, it is preferably themeta-position. m is an integer of 0 to 4, and more preferably 0 to 2.

Examples of a halogen atom include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom. Examples of a hydrocarbyl group having1 to 10 carbon atoms include more preferably a linear or branched alkylgroup, alkenyl group, or alkynyl group having 1 to 6 carbon atoms, andfurther preferably a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, a n-pentyl group, and a n-hexyl group. The alkylthiogroup having 1 to 10 carbon atoms is more preferably an alkylthio grouphaving 1 to 6 carbon atoms, and examples thereof include a methylthiogroup, an ethylthio group, an n-propylthio group, an isopropylthiogroup, a n-butylthio group, an isobutylthio group, a sec-butylthiogroup, a tert-butylthio group, a n-pentylthio group, and a n-hexylthiogroup. The alkylamino group having 1 to 10 carbon atoms is morepreferably an alkylamino group having 1 to 6 carbon atoms. Thealkylamino group is preferably a dialkylamino group, and the alkylssubstituting amino groups may be the same or different alkyls. Morepreferable examples of the alkylamino group include a dialkylaminogroup, such as a dimethylamino group, a diethylamino group, adi-n-propylamino group, a diisopropylamino group, a di-n-butylaminogroup, a diisobutylamino group, a di-sec-butylamino group, and adi-tert-butylamino group. The alkoxy group having 1 to 10 carbon atomsis more preferably an alkoxy group having 1 to 3 carbon atoms, andexamples thereof include a methoxy group, an ethoxy group, and a propoxygroup. Examples of a saturated condensed ring formed by mutual bindingof R⁴s and condensation with the aromatic ring substituted with the R⁴include a naphthalene ring. Examples of the hetero-condensed ring formedby mutual binding of R⁴s and condensation with the aromatic ringsubstituted with the R⁴ include an indole ring, an isoindole ring, aquinoline ring, an isoquinoline ring, a carbazole ring, an acridinering, a benzofuran ring, a benzopyran ring, and a benzothiophene ring.The condensed ring may have 1 to 6 substituents, and the substituentsare the same as R⁴ above.

Specific examples of the compound represented by the general formula(II) include, but not limited to, a substituted 2-allylanisole(hereinafter also referred to as “APR”), such as2-allyl-4-fluoroanisole, 2-allyl-4,5-difluoroanisole,2-allyl-4-methylanisole, 2-allyl-4-tert-butylanisole,2-allyl-4-hexylanisole, 2-allyl-4-methoxyanisole, and3-(2-methoxy-1-naphthyl)-1-propyl ene; and unsubstituted 2-allylani sole(3-(2-ani syl)-1-propylene) (hereinafter also referred to as “AP”).

The polar olefin monomers may be used singly in a polymerizationreaction, or in combination of two or more kinds thereof

(Nonpolar olefin monomer)The polar olefin monomer may be copolymerized with another monomer(preferably nonpolar olefin monomer). There is no particular limitationon a nonpolar olefin monomer, insofar as it is capable ofaddition-polymerization, and copolymerization with a polar olefinmonomer. Examples thereof include ethylene, α-olefin, a substituted andunsubstituted styrene, a diene, and a cyclic olefin having 3 to 20carbon atoms (including a norbornene, such as 2-norbornene anddicyclopentadiene, and cyclohexadiene).

Specific examples of the α-olefin include a linear α-olefin having 3 to20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, and 1-eicocene; and a branched α-olefin having 4 to 20carbon atoms, such as 4-methyl-1-pentene, 3-methyl-1-pentene, and3-methyl-1-butene. Examples of the diene, which is an olefinic monomer,include a linear diene having 3 to 20 carbon atoms, such as1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene,1,4-hexadiene, 1,5-hexadiene and 2,4-hexadiene; a branched diene having4 to 20 carbon atoms, such as 2-methyl-1,3-butadiene,2,4-dimethyl-1,3-pentadiene, and 2-methyl-1,3-hexadiene; and a cyclicdiene having 4 to 20 carbon atoms, such as cyclohexadiene.

The nonpolar olefin monomers singly may be used singly in apolymerization reaction, or in combination of two or more kinds thereof

The polar olefin monomer, or nonpolar olefin monomer may be synthesizedand used based on a method common in the field of organic chemistry.Alternatively, a commercially available one may be used.

<Polar olefin-based polymer>An olefin-based molded product of the present invention contains a polarolefin-based polymer that is a polymer including a structural unit of atleast one polar olefin monomer represented by the general formula (I).A polar olefin polymer used as a raw material for an olefin-based moldedproduct of the present invention includes the structural unit of polarolefin monomer preferably at 20 mol % or more, more preferably 30 mol %or more, 40 mol % or more, 50 mol % or more, 60 mol % or more, 70 mol %or more, or 80 mol % or more in terms of molar ratio.Although the molecular weight distribution of a polymer is arbitrary, apolymer having a relatively narrow polymer molecular weight distributioncan also be used favorably. In this regard, the molecular weightdistribution may be a value (Mw/Mn) measured by a GPC method (measuredat 145° C. using polystyrene as a standard substance, and1,2-dichlorobenzene as an eluent), or the like, which may be measured,for example, using a GPC measuring device (TOSOH HLC 8321 GPC/HT).The molecular weight distribution of a polymer in terms of Mw/Mn as anindex is usually 5.0 or less, and preferably 4.0, or less, or 3.0 orless.

The number average molecular weight of a polymer is arbitrary, and apolymer having a relatively high number average molecular weight ofpolymer can also be favorably used. Although the number averagemolecular weight (g/mol) varies depending on the structure of astructural unit derived from the polar olefin monomer, the proportion ofa structural unit derived from the polar olefin monomer, or the like, itis usually 2.0×10³ or higher, and preferably 3.0×10³ or higher, 10×10³or higher, 50×10³ or higher, 80×10³ or higher, 100×10³ or higher,150×10³ or higher, 200×10³ or higher, 250×10³ or higher, 300×10³ orhigher, 350×10³ or higher, 400×10³ or higher, 450 ×10³ or higher,500×10³ or higher, or 1000×10³ or higher from the viewpoint of achievinga high level of mechanical characteristics as described above,autonomous self-healing function, or characteristics such asshape-memory property.

The glass transition point (Tg) of a polymer may vary depending on thestructure of the structural unit derived from a polar olefin monomer.Although the glass transition point is not particularly limited, it isusually about −40 to 100° C. A glass transition point can be measured bydifferential scanning calorimetry (DSC) or the like. For obtaining aself-healing molded product, the Tg of the polymer used as a rawmaterial is preferably not higher than room temperature (generally 25°C., which may vary depending on the utilized mode and conditions). Forobtaining a shape-memory molded product, the Tg of the polymer used as araw material is preferably higher than room temperature (generally 25°C., which may vary depending on the utilized mode and conditions).

When a polymer has a melting point, it may vary depending on thestructure of the structural unit derived from a polar olefin monomer,the proportion of the structural unit derived from a polar olefinmonomer, or the like, however it is usually 100° C. or higher, andpreferably 110° C. or higher, 120° C. or higher, or 130° C. or higher. Amelting point can be measured by, for example, the differential scanningcalorimetry (DSC).

As an embodiment of the polar olefin-based polymer, a copolymer of thepolar olefin monomer and ethylene (nonpolar olefin monomer) will beexemplified. The copolymer is a copolymer including a structural unitderived from a polar olefin monomer represented by the following formula(A), and a structural unit derived from ethylene represented by theformula (B).

In this regard, Z, R¹, R², and n in the formula (A) are the same as Z,R¹, R², and n described above in connection with the general formula(I).

In the copolymer, the structural units respectively represented by theabove formulas (A) and (B) may be aligned in any order. That is, bothmay be aligned at random, or aligned with some regularity (for example,the structural units of (A) and (B) are alternatingly aligned, someunits of each are aligned serially, or they may be aligned in anotherfixed order). Therefore, the copolymer may be a random copolymer, analternating copolymer, a block copolymer, or another ordered copolymer.The copolymer is preferably an alternating copolymer.

An alternating copolymer is constituted with the main sequence in whichthe structural units of (A) and (B) are aligned alternatingly(hereinafter also referred to as “alternating (A)—(B) sequence” or“(A)—alt—(B) sequence”), but it may in some cases include as asub-sequence a sequence in which two to several of the respective unitsare aligned serially. The copolymer is an alternating copolymer, and theproportion of the alternating (A)—(B) sequence in the total sequences ofthe copolymer (in a case where two or more kinds of structural units ofpolar olefin monomers and two or more kinds of structural units ofnonpolar olefin monomers are included, the proportion of the totalalternating sequences constituted with structural units of the polarolefin monomers and structural units of the nonpolar olefin monomers) interms of molar ratio is usually 30 mol % or more, and preferably 40 mol% or more, 50 mol % or more, 60 mol % or more, or 70 mol % or more.

More specifically, in the embodiment of an alternating polymer, inaddition to the alternating sequence —(A)—alt—(B)—, polymerizationsequence of each of (A) or (B) may be included. When the polymerizationsequence of (B), i.e. —(B)—(B)—. is included together with thealternating sequence —(A)—alt—(B)—, this constitution conceivablycontributes to development of functionality of the molded product of thepresent invention, as described later. The proportion of thepolymerization sequence of (B) (—(B)—(B)—) with respect to the totalsequences of the copolymer (in a case where structural units of two ormore kinds of nonpolar olefin monomers are included, a random copolymer,an alternating copolymer, a block copolymer, or another orderedcopolymer constituted with structural units of two or more kinds ofnonpolar olefin monomers is also included) in terms of molar ratio isusually 60 mol % or less, and preferably 50 mol % or less, 40 mol % orless, 30 mol % or less, or 20 mol % or less. Meanwhile, the proportionof the polymerization sequence of (A), i.e. —(A)—(A)—. with respect tothe total sequences of the copolymer (in a case where structural unitsof two or more kinds of polar olefin monomers are included, a randomcopolymer, an alternating copolymer, a block copolymer, or anotherordered copolymer constituted with structural units of two or more kindsof polar olefin monomers is also included) in terms of molar ratio ispreferably 20 mol % or less, 10 mol % or less, 5 mol % or less, or 3 mol% or less, and may be even 0 mol %.

The proportion of the sequence can be measured, for example, by ¹H-NMR,or ¹³C-NMR. Specifically, it can be determined by comparing theintegration ratios of peaks between 1.0 and 1.5 ppm by ¹H-NMR.

The percentage of the structural unit of formula (A) or the structuralunit of formula (B) included in the copolymer is arbitrary. For example,the proportion of the structural unit of formula (A) with respect to thetotal structural units in terms of molar ratio may be from 1 to 99 mol%. Further, by the above production method, a copolymer having arelatively high proportion of the structural unit of polar olefinmonomer therein can be also prepared.

It is considered that in an olefin-based molded product of the presentinvention, in which the proportion of the structural unit of formula (A)is adequately high, the proportion of the alternating sequence (A)—(B)can be made adequately high, and consequently characteristics such asautonomous self-healing function, excellent mechanical properties, andshape-memory property can be exhibited. It is considered that anolefin-based molded product of the present invention can have anautonomous self-healing function, and a higher toughness owing to suchcharacteristics of the copolymer. It can be said that to have suchmechanical properties as high toughness is equivalent to well-balanceddevelopment of high enough tensile strength and high enough elongationat break. The proportion of the structural unit of polar olefin monomerin a copolymer, in terms of molar ratio the structural unit of formula(A) is usually 20 mol % or more, and preferably 30 mol % or more, 40 mol% or more, 50 mol % or more, 60 mol % or more, 70 mol % or more, or 80mol % or more, from the viewpoints of achieving the aforedescribedcharacteristics such as high mechanical properties, autonomousself-healing function, and shape-memory property.

The proportion of the structural unit can be measured by, for example,¹—H-NMR, or ¹³C-NMR. Specifically, it can be determined by ¹H-NMR bycomparing the integration ratio of methylene or methyl hydrogen adjacentto a hetero atom with that of a hydrocarbon present between 1 and 1.8ppm. The proportion of the structural unit can be regulated by adjustingthe ratio between each monomer that is a raw material in the productionof the copolymer.When the percentage of the structural unit of formula (A) is increased,favorable features of a polar group of the polar olefin monomer, such asthe adhesiveness or compatibility with polar materials, can beeffectively developed. Further, since the copolymer can be made to havea higher molecular weight, the entanglement points are increased, sothat advantageous improvement of the compatibility or adhesiveness canbe expected.

Although the molecular weight distribution of a copolymer is arbitrary,a copolymer having a relatively narrow copolymer molecular weightdistribution can also be used favorably. In this regard, the molecularweight distribution may be a value (Mw/Mn) measured by a GPC method(measured at 145° C. using polystyrene as a standard substance, and1,2-dichlorobenzene as an eluent), or the like, which may be measured,for example, using a GPC measuring device (TOSOH HLC 8121 GPC/HT).

The molecular weight distribution of a copolymer in terms of Mw/Mn as anindex is usually 5.0 or less, and preferably 4.0 or less, or 3.0 orless.

The number average molecular weight of a copolymer is arbitrary, and acopolymer having a relatively high number average molecular weight ofcopolymer can also be favorably used. Although the number averagemolecular weight (g/mol) varies depending on the structure of astructural unit derived from the (non)polar olefin monomer, theproportions of a structural unit derived from the polar olefin monomerand a structural unit derived from the nonpolar olefin monomer, or thelike, the number average molecular weight is usually 2.0×10³ or higher,and preferably 3.0×10³ or higher, 10×10³ or higher, 50×10³ or higher,80×10³ or higher, 100×10³ or higher, 150×10³ or higher, 200×10³ orhigher, 250×10³ or higher, 300×10³ or higher, 350×10³ or higher, 400×10³or higher, 450×10³ or higher, 500×10³ or higher, or 1000×10³ or higherfrom the viewpoint of achieving a high level of mechanicalcharacteristics, autonomous self-healing function, or characteristicssuch as shape-memory property.

The glass transition point (Tg) of a copolymer may vary depending on thestructure of the structural unit derived from a polar olefin monomer.Although the glass transition point is not particularly limited, it isusually about −40 to 100° C. A glass transition point can be measured bydifferential scanning calorimetry (DSC) or the like. For obtaining aself-healing molded product, the Tg of the copolymer used as a rawmaterial is preferably not higher than the service temperature (forexample, when the service temperature is room temperature it isgenerally 25° C., which may however vary depending on the utilized modeand conditions). For obtaining a shape-memory molded product, the Tg ofthe copolymer used as a raw material is preferably higher than theservice temperature (for example, when the service temperature is roomtemperature it is generally 25° C., which may however vary depending onthe utilized mode and conditions).

When a copolymer has a melting point, it may vary depending on thestructure of the structural unit derived from a (non)polar olefinmonomer, the proportions of the structural unit derived from a polarolefin monomer and the structural unit derived from a nonpolar olefinmonomer, or the like, however it is usually 100° C. or higher, andpreferably 110° C. or higher, 120° C. or higher, or 130° C. or higher. Amelting point can be measured by, for example, differential scanningcalorimetry (DSC).

One embodiment of the copolymer according to the present inventionincludes structural units respectively represented by the followingformulas (III) and (IV). In the formula, x and y represent theproportion (molar ratio) of each structural unit with respect to thetotal sequences in the copolymer.

In the formula, R¹, R³, R⁴, Z, m and n respectively have the samemeanings as in the formula (II), and the same applies to the preferableranges. Each of x and y stands for the proportion of each structuralunit, and is a positive number that satisfies x>0, y >0, x>y, and80%<x+y<100%. The x+y is preferably 85% or more, 90% or more, 95% ormore, or 97% or more.

<Olefin-Based Molded Product>

An olefin-based molded product of the present invention is anolefin-based molded product comprising at least one polymer of a polarolefin monomer represented by the general formula (I). An embodiment ofthe olefin-based molded product of the present invention has analternating ethylene—(substituted) anisylpropylene sequence, anddevelops an autonomous self-healing function and excellent mechanicalproperties. Concerning the mechanism for the development of theautonomous self-healing function and excellent mechanical properties, itis considered that a polar olefin copolymer has an alternatingethylene—(substituted) anisylpropylene, and (substituted) anisyl groupsare regularly distributed as side chains in the skeleton of analternating ethylene—propylene copolymer. This may have enhancedentanglement of molecules between damaged faces and polymer chainswithout being seriously affected by water, an acid, or a base. In anembodiment of the olefin-based molded product of the present invention,self-healing without the need for external energy or stimulation(pressure, temperature, etc.), namely autonomous self-healing ispossible not only in air but also in water, or an acid or basicsolution. Although for the self-healing function of the olefin-basedmolded product of the present invention, external energy or stimulation(pressure, temperature, etc.) is not particularly required, they may beapplied also. When external energy or stimulation (pressure,temperature, etc.) is applied, advantages such as acceleration of theself-healing speed may be expected.

In this regard, “self-healing” means return to the shape and physicalproperties before the damage, for example, by bringing damaged parts,such as a flaw of a molded product or cut surfaces, in contact with eachother to regenerate entanglement of copolymer chains.

A self-healing function can be confirmed by comparing the shape andphysical properties after the damage and after bringing damaged parts incontact with each other, and allowing them to stand at a predeterminedtemperature in a predetermined environment for a predetermined time,with the same before the damage. Specifically, it can be confirmed, forexample, by the method described in Example below. The self-healingefficiency of the olefin-based molded product of the present inventionvaries depending on the kind of a copolymer used, or the like, and isnot particularly limited. For example, in the self-healing testaccording to the method described in Example below, in which damagedparts of the olefin-based molded product are brought into contact witheach other, and left standing at room temperature (for example, 25° C.)in air to make self-healing occur autonomously, the elongation at breakafter the damage with respect to the elongation at break before thedamage becomes usually 50% or more, and preferably 60% or more, 70% ormore, 80% or more, 90% or more, 95% or more, 99% or more, and 100%.

One embodiment of a self-healing molded product is a molded productcontaining the copolymer, which includes structural units represented bythe formulas (III) and (IV) respectively, and has a Tg of not higherthan the service temperature (for example, if the service temperature isroom temperature, it is generally 25° C.).

With respect to an embodiment of a molded product of the presentinvention to be used as a self-healing material, a self-healing rate of80% or more is achievable.

There is no particular limitation on the time required for achievingsuch self-healing rate, and it may be adjusted depending on the kind ofpolymer used (more specifically, on the kind of the substituent of thebenzene ring in the formula (III), the ranges of x and y, and themolecular weight, in the embodiment containing a copolymer includingstructural units represented by the formulas (III) and (IV)respectively), or the like. In one example, a self-healing rate of 80%or more can be achieved in 5 days.

One embodiment of the olefin-based molded product of the presentinvention is an olefin-based molded product having a shape-memoryfunction.

In this regard, the “shape-memory function” means a nature that, when aprimarily shaped olefin-based molded product is deformed by an externalforce at a temperature below the temperature at which primary shapingwas conducted but not below the glass transition temperature, and thedeformed shape is fixed (secondary shaping) at a temperature not abovethe glass transition temperature, the olefin-based molded product keepsthe secondary shape at a temperature not above the glass transitiontemperature, but returns to (recovers) the primary shape when it isheated to a temperature of the glass transition temperature or higherunder no-load.

The shape-memory function can be confirmed by, for example, deforming anolefin-based molded product at a predetermined temperature, keeping itin the deformed state, and allowing it to recover, and comparing theshape after recovery with that before deformation. Specifically, it canbe confirmed, for example, by the method described in Example below. Theshape fixed rate and the shape recovery rate showing the shape-memoryperformance can be calculated based on the change of the rate ofelongation by a thermomechanical analysis (TMA). The former can becalculated as the ratio (E2′/E2) of the rate of elongation E2′ whenfixed at a temperature below Tg to the rate of elongation E2 immediatelyafter deformation at a temperature of Tg or higher. The shape recoveryrate can be calculated as the ratio (E1′/E1) of the rate of elongationE1′ recovered at a temperature of Tg or higher through the deformationand fixation to the rate of elongation E1 returning to the originalshape. Specifically, they are values that can be calculated from theresults of thermal analysis. For example, FIG. 40 described later showsthat a sample was heated to 50° C., stretched by 100%, and then cooledto 0° C. to fix the sample in that state realizing a shape fixed rate of99.5%. Further, it shows that the tensile load was then removed to zeroand the sample was heated to 50° C. allowing it to heal realizing ashape fixed rate of 99.1%.

In an embodiment of the shape-memory molded product, it maintains aconstant shape S1 at a service temperature Tu (for example, roomtemperature), it can be deformed to the shape S2 by applying an externalforce at a temperature Td higher than Tg (Tu<Tg) (and when there is amelting point, at a temperature below the melting point), it canmaintain the the shape S2 when it is cooled to the service temperatureTu in the shape S2, and can be used in the shape, and it has ability toreturn to the original shape S1 at the temperature Tr (Tr may be thesame as or different from Td) which exceeds Tg (and below the meltingpoint, when it has one). In other words, the embodiment of theshape-memory molded product can be easily deformed to a shape S2different from the original shape S1 by applying an external force at atemperature Td which exceeds Tg (Tu<Tg), and when it is cooled to Tu,the shape S2 is maintained to manifest the shape fixing property (Rf),and when it is heated to a temperature Tr which exceeds Tg (Tu<Tg)without applying any external force, the shape is returned to theoriginal shape S1 to manifest also the shape recovering property(R_(r)). An embodiment of a shape-memory molded product is a moldedproduct containing a copolymer, which includes structural unitsrepresented by the formulas (III) and (IV) respectively, and has a Tg ashigh as the service temperature (for example, when the servicetemperature is room temperature about room temperature (e.g., 15° C. to35° C.)), or beyond the service temperature.

One embodiment of a molded product of the present invention used as ashape-memory material can achieve a shape fixed rate and a shaperecovery rate of 50% or more respectively, and can preferably achieve80% or more, respectively.

Polar olefin-based polymers contained in an olefin-based molded productof the present invention cover a wide glass transition temperaturerange, and exhibit at room temperature (for example, 25° C.) a varietyof mechanical properties (rigid plastic, flexible plastic, elastomer, orstress softening material) depending on the glass transitiontemperature. For example, as described in Examples below, P5 having aglass transition temperature of 6° C., P7 of 4° C., and P8 of 11° C. areelastomers at room temperature (FIG. 33A). This elastomer exhibitsexcellent mechanical properties, and particularly superior in toughness,tensile strength, and elongation at break.

The toughness value of an olefin-based molded product varies dependingon the kind of a polymer used (more specifically, in an embodimentcontaining a copolymer including structural units represented by theformulas (III) and (IV) respectively, the kind of a sub stituent of thebenzene ring in the formula (III), the ranges of x and y, and themolecular weight), or the like, and is not particularly limited. It maybe adjusted to an appropriate range depending on the intended use. Whena polar olefin-based polymer having a larger molecular weight (Mn) isused as a raw material, the toughness value of the obtained moldedproduct tends to increase. For example, by a measurement at atemperature not below the glass transition temperature where the polymerexhibits a rubber state (as an example, room temperature (for example,25° C.)), the toughness of a molded product of the present inventionusually exceeds 0.25 MJ/m³, and 0.5 MJ/m³ or more is achievable. Foryielding a self-healing molded product, the toughness is preferably 1MJ/m³ or more, 5 MJ/m³ or more, 10 MJ/m³ or more, 20 MJ/m³ or more, or30 MJ/m³ or more. Not limited to room temperature, an embodiment whichexhibits a toughness within the above range at the service temperatureof the molded product is also acceptable.

The tensile strength of the olefin-based molded product varies dependingon the kind of a polymer used (more specifically, in an embodimentcontaining a copolymer including structural units represented by theformulas (III) and (IV) respectively, the kind of a sub stituent of thebenzene ring in the formula (III), the ranges of x and y, and themolecular weight), or the like, and is not particularly limited. It maybe adjusted to an appropriate range depending on the intended use. Whena polymer having a higher glass transition point is used as a rawmaterial, the tensile strength of the obtained molded product tends toincrease. For example, by a measurement at a temperature not below theglass transition temperature where the polymer exhibits a rubber state(as an example, room temperature (for example, 25° C.)), the moldedproduct of the present invention can achieve 0.1 MPa or higher. Thetensile strength is preferably higher than 0.4 MPa, 0.5 MPa or more, 1MPa or more, 10.0 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa ormore, or 50 MPa or more. Not limited to room temperature, an embodimentwhich exhibits a tensile strength within the above range at the servicetemperature of the molded product is also acceptable.

The elongation at break of the olefin-based molded product variesdepending on the kind of a polymer used (more specifically, in anembodiment containing a copolymer including structural units representedby the formulas (III) and (IV) respectively, the kind of a sub stituentof the benzene ring in the formula (III), the ranges of x and y, and themolecular weight), or the like, and is not particularly limited. It maybe adjusted to an appropriate range depending on the intended use. Whena polymer having a higher glass transition point is used as a rawmaterial, the elongation at break of the obtained molded product tendsto decrease. For example, by a measurement at a temperature not belowthe glass transition temperature where the polymer exhibits a rubberstate (as an example, room temperature (for example, 25° C.)), themolded product of the present invention can achieve about 10% or more.For yielding a self-healing molded product, the elongation at break ispreferably more than 100%, 500% or more, 1000% or more, 1200% or more,1500% or more, or 2000% or more. For stably obtaining a self-healingability, the upper limit value is about 10000%. Not limited to roomtemperature, an embodiment which exhibits an elongation at break withinthe above range at the service temperature of the molded product is alsoacceptable.

The mechanical properties of a polar olefin-based polymer can bemeasured by a conventional tensile test. Specifically, for example, thetest is conducted using the method described in Example below (using adumbbell specimen (width: 2 mm; length: 12 mm; thickness: 1 mm) based onJIS K-6251-7 according to the test method of ASTM 882-09). A breakingstress-breaking strain test is based on fracture using a uniaxialtensile test with a strain rate of 200 mm/min. A toughness value can becalculated by calculating the area of the stress-strain curve.

The olefin-based molded product of the present invention may be anolefin-based molded product containing a polar olefin-based polymer as amain component (50% by mass or more), or an olefin-based molded productcontaining it as a subcomponent (less than 50% by mass). A polymericmaterial such as a (co)polymer other than a polar olefin-based polymer,as well as various additives usually used for a molded product, such asan excipient, a lubricant, a UV absorbent, a weathering stabilizer, anantistatic agent, an antioxidant, a heat stabilizer, a nucleating agent,a flow improver, and a colorant, may be included.

The olefin-based molded product of the present invention is preferablyproduced by melt-molding a polar olefin-based polymer. The melt moldingmay be performed by a publicly known method. Examples of such meltmolded product include, but not limited to, an injection molded product,a vacuum, or air pressure formed product, an extrusion molded product, ablow molded product, a hot press (melt press) molded product, and a castmolded product; and specifically pellet, fiber and cloth, film, sheet,and non-woven fabric. In addition, a molded product can be producedusing laser processing, 3D printer technology, or the like.

(Film)

The present invention also relates to a film containing the polarolefin-based polymer. An embodiment of the film is a transparent film. Afilm which is one of the olefin-based molded products of the presentinvention can be formed by a publicly known method. For example, amolding method such as extrusion molding, hot press molding, and castmolding can be used. In the case of extrusion molding, a molten filmmaterial is extruded by using an extruder equipped with a T die, acircular die, or the like, and optionally further stretched orheat-treated to form a film.

In the case of hot press molding, a molten film material is pressed andcooled by using a hot plate press or the like, and optionally furtherstretched or heat-treated to form a film.

Also, an unstretched film is cast-molded by dissolving, casting, anddrying and solidifying using a cosolvent for the film material, whichmay be optionally further stretched or heat-treated.

The formed unstretched film can be used as it is. As the film material,a material in which a polar olefin-based polymer and the aforedescribedvarious additives are melt-kneaded in advance may be used, or these maybe melt-kneaded while molding is carried out.

The unstretched film can be longitudinally uniaxially stretched in themachine direction, or transversely uniaxially stretched in thecross-machine direction. Also, a biaxially stretched film can beproduced by stretching by a successive biaxial stretching method withroll stretching and tenter stretching, a simultaneous biaxial stretchingmethod with tenter stretching, a biaxial stretching method by tubularstretching, or the like. This film may be further subjected normally toa heat-fixing treatment after stretching in order to suppress heatshrinking, or the like. The obtained film may be optionally subjected toa surface activation treatment, or the like according to a publiclyknown method. Further, after being formed to a continuous long film, itmay be stored/transported in a rolled-up state.

The film of the present invention may be used as it is as a moldedproduct, or it may be used in combination with another kind of film orthe like. Examples of the form of the combination include a combinationwith another kind of film, such as a layered body and a laminate as wellas a combination with another molded product by overlaying or otherwise.

The state of the polymer in a molded product (for example, film) of thepresent invention is schematically shown in FIG. 36B. In the figure, acurve represents an alternating sequence chain —(A)—alt—(B)— of a polarolefinic monomer (A) such as anisylpropylene and a nonpolar olefinicmonomer (B) such as ethylene; and a circle represents a crystallinenanodomain formed with homopolymerization sequences —(B)—(B)— of anonpolar olefinic monomer (B) such as ethylene. Short chain —(B)—(B)—segments present in the copolymer according to the present invention areconceivably aggregated in a molded product (for example, film) to form alarge number of crystalline nanodomains. This can be understood from thefact that an X-ray diffraction peak attributed to (110) plane of anorthorhombic crystal appears in a WAXD analysis. The mechanism by whicha molded product of the present invention exhibits a unique self-healingability is presumed as follows. In a molded product of the presentinvention, crystalline nanodomains are distributed in the matrix offlexible alternating sequence chains (—(A)—alt—(B)—), in which thecrystalline nanodomains conceivably function as physical cross-linkingpoints connecting flexible alternating sequence chains (—(A)—alt—(B)—).When a molded product sustains a mechanical damage, a crack or the likeoccurs to destroy partially the matrix of alternating sequence chains.It is considered however that repair of the damaged part progresses byre-aggregation of the crystalline nanodomains to facilitatereconstruction of the network structure of alternating sequence chains(—(A)—alt—(B)—).

The present invention also relates to a coating composition containingat least one kind of the (co)polymer according to the present invention.The coating composition can be used to form a film on various surfaces.The coating composition may include a liquid medium (either an aqueoussystem or an organic solvent system), or a solid medium together withthe polymer. In an embodiment containing a medium, the polymer may be ina state dissolved in the medium, or in a non-dissolved (for example,dispersed) state. The performance, such as self-healing ability, derivedfrom the polymer may be imparted to a part or all of the surface of anarticle, by applying the coating composition to at least a part of thesurface of the article, and, if necessary, removing a medium by drying,to form a film.

EXAMPLES

The present invention will be specifically described below withreference to Examples, provided that the present invention is notlimited to the embodiments of the following Examples.

The present invention will be described below in detail with referenceto Examples, provided that the scope of the present invention is notlimited in any way by the following.

<Metallocene Complex>

The metallocene complexes used in Examples were synthesized according tothe methods described in the following literature.

(1) X. Li, M. Nishiura, K. Mori, T. Mashiko, Z. Hou, Chem. Commun.,4137-4139 (2007)

(2) F. Guo, M. Nishiura, H. Koshino, Z. Hou, Macromolecules, 44,6335-6344 (2011).

The metallocene complexes used in Examples are as follows:

Complex 1: (C₅H5)Sc(CH2C₆H4NMe2-o)₂

Complex 2: (C₅Me₄SiMe₃)Sc(CH₂Cl₆H₄NMe₂—O₂

The structures of the metallocene complexes used in Examples are shownin FIG. 1 .

<Ionic Compound>

[Ph₃C][B(C₆F₅)₄] (97%) was purchased from Strem Chemical Corporation andused without purification.

<Monomer>

All monomers were purified before use by distillation from Al(octyl)₃(25 wt % in hexane), and Na, or by recrystallization from hexane. Thestructures of the polar olefin monomers used in Examples are shown inFIG. 2 .

<Measurement Method> (NMR)

The NMR data of a polymer was measured using a Bruker AVANCE III HD 500NMR spectrometer (FT, 500 MHz: ¹ H; 125 MHz: ¹³C) and CD₂Cl₂ (26.8° C.)or 1,1,2,2-C₂D2C₁₄ (120° C.) as a solvent. A measurement of ¹H NMR wasperformed using tetramethylsilane (TMS) as the internal standard, andthe chemical shifts of the respective solvents are as follows (7.26 ppm:CDCl₃, 7.16 ppm: C₆D₆, 5.32 ppm: CD₂C₁₂, and 6.0 ppm: 1,1,2,2-C₂D2C₁₄).Chemical shifts of ¹³C NMR were reported with reference to the peak ofeach solvent [CDCl₃ (77.16 ppm), CD₂C₁₂ (53.84 ppm), 1,1,2,2-C₂D2C₁₄(73.78 ppm), or C₆D6 (128.06 ppm)]. Coupling constants (J) are shown interms of Hz, which indicate overlap of the separated peaks. Theabbreviations s, d, t, q, and m indicate singlet, doublet, triplet,quartet, and multiplet in each order.

(Gel Permeation Chromatography (GPC) Measurement)

The molecular weight and molecular weight distribution of a copolymerwere determined by high temperature gel permeation chromatography(HT-GPC) at 145° C. using an HLC-8321GPC/HT device (Tosoh Corporation).The flow rate was set at 1.0 mL/min using 1,2-dichlorobenzene (DCB) asthe eluting solvent. Calibration was performed using polystyrenestandards (Tosoh Corporation).

(Differential Scanning Calorimetry (DSC) Measurement)

A DSC measurement was performed with a DSC 6220 (SII Corporation) at aspeed of 10° C./min (unless otherwise specified). The thermal historyerror in a polymer was removed by heating a sample to 150° C. for thefirst time, cooling down at 10° C./min to about −100° C., and recordingthe second DSC scan (unless otherwise specified).

(Preparation of Film)

A copolymer film was prepared by melt-pressing at 160° C. under apressure of 30 MPa for 5 min, and cooling down to 22° C. at 10° C./hour.

(Tensile Test>

The mechanical tensile stress test was performed using an Instron 3342device (Instron). Three samples were tested for each polymercomposition. The tensile test was conducted at room temperature (25±1°C.) by the test method according to ASTM 882-09 using a dumbbellspecimen (width: 2 mm; length: 12 mm; thickness: 1 mm) according to JISK-6251-7 (when the elasticity was evaluated, a different specimen sizeand strain rate were applied). The breaking stress—breaking strain testwas carried out by causing a fracture by means of a uniaxial tensiletest at a strain rate of 200 mm/min. Young's modulus was defined as theinitial slope of the linear region (0<c<0.05) in a nominalstress—nominal strain curve, and calculated as the average of 3 monotonecurves. A toughness value was determined by calculating the area of thestress-strain curve. The stress-strain cycle test was performed at astrain rate of 200 mm/min and a release rate of 20 mm/min. The strainrecovery was determined by a 1000% strain cycle test according to theformula: 100(c_(a)-cr)/c_(a), where E_(a)=applied strain, and Er=strainwithout load after 10 cycles.

<Self-Healing Test>

As a self-healing test, a sample was cut into completely separateportions using a razor blade. The fractured surfaces of the film wereallowed to be jointed for different time durations in air, water, a HClaqueous solution, and a NaOH aqueous solution. In other words, the cutfaces were jointed and pressed lightly for about 15 sec, and thenallowed to heal at 25° C. for each time duration. The stress-straincurves were obtained by the above method for the healed copolymer films.The mechanical repair efficiency η was determined as the ratio of thehealed fracture strain to the original fracture strain.

[Example 1] Copolymerization of 2-Allylanisole (AP) with Ethylene (Table1, Run 3)

In a glove box, a toluene solution (1.0 mL) of [Ph₃C][B(C₆F₅)₄] (9.3 mg,10 μmol) was added gradually to a toluene solution (1.0 mL) of(C₅Me4SiMe3)Sc(CH2C₆H4NMe2-o)₂ (complex 2, 5.1 mg, 10 μmol) in a 10 mLglass tube under stirring with a magnetic stirrer. AP (0.74 g, 5.0 mmolin 150 mL toluene) was charged into a three necked flask. The flask wastaken out, placed in a water bath (25° C.), and connected with anethylene Schlenk line and a mercury sealed valve which were thoroughlycleaned by purging using a three-way cock. Ethylene was introduced intothe system and the solution was stirred for 1 min to be saturatedtherewith. A catalyst solution was added using a sealed syringe undervigorous stirring. When the viscosity of the reaction solution increased(5 min), methanol (50 mL) was added to stop the polymerization reaction.The polymer was recovered by filtration, washed with methanol, and driedunder reduced pressure at 60° C. for 24 hours to yield a colorlessrubbery substance (0.91 g). The measurement results of the physicalproperties of the yielded polymer are shown in Table 1.

As shown in Table 1, the complex, the ratio of the monomer to thecatalyst, the reaction time, etc. were changed, and the polymerizationreaction was performed in the same manner as the copolymerization of APand ethylene described above. The measurement results of the physicalproperties of the obtained polymers are shown in Table 1 and FIGS. 3 to6 .

With Complex 1 a copolymer was not yielded, but a highly syndiotactichomopolymer was yielded. This is presumably because the the AP monomerwas preferentially coordinated with the complex 1 due to use of acatalyst having sterically small ligands, and its polymerizationproceeded. When a sterically bulky Complex 2 was used, a copolymerproduct (P1) of ethylene—2-allylanisole (E-AP) was exclusively obtained(Table 1, run 2). Setting E at 1 atm, as the [O]/[M] ratio was increasedfrom 200/1 to 500/1, 1000/1, 2000/1, and 5000/1, the number averagemolecular weights (Mn) of the obtained copolymers (P1 to P5) wereincreased remarkably, while the introduction rates of the AP monomerinto the copolymer were maintained with a slight increase (Table 1, runs2 to 6).

It was shown by a ¹³C{¹H} NMR analysis, that the copolymers (P1 to P5)mainly had an alternating AP-E sequence (67 to 76%), together with someAP-(E)_(n)-AP sequence (n≥2, 19 to 33%), and E-AP-AP-E sequence (0 to5%). In the following formulas, each copolymer was schematicallyexpressed only by an alternating AP-E sequence, which was the mainsequence. Further, the copolymers (P1 to P5) were amorphous and had aglass transition temperature.

The reason why the copolymer having the aforedescribed unique structurewas obtained with the complex 2 is presumably that the copolymerizationproceeded according to the following scheme. In the following scheme,the counter anion [B(C₆F₅)₄]⁻was omitted.

TABLE 1

Activity M_(n) Yield (g mol-Sc⁻¹h⁻¹ (10³ g Run^(a) [M] [O]/[M]^(b)(g)^(c) Time atm⁻¹) mol⁻¹)^(d) M_(w)/M_(n) ^(d) AP/E^(e) T_(g) ^(f)1^(h) 1  200/1 0.20 10 min —  5 1.65 100/0h   60 2^(g) 2  200/1 0.70 15min 1.4 × 10⁵  41 (P1) 1.68  39/61  −8 3 2  500/1 0.91  5 min 1.1 × 10⁶ 90 (P2) 1.58  39/61  −6 4 2 1000/1 1.61 15 min 6.4 × 10⁵ 173 (P3) 1.94 41/59    4 5 2 2000/1 3.05  6 h 5.1 × 10⁴ 344 (P4) 1.70  45/55    5 6 25000/1 8.35 24 h 3.5 × 10⁴ 552 (P5) 1.98  46/54    6 ^(a)Condition: [M](0.01 mmol). [Ph3C][B(C6F5)4] (B) (0.01 mmol), ethylene (1 atm), 150 mLtoluene, 20° C. (unless otherwise specified) ^(b)Feed ratio (mole) of APto scandium complex ^(c)Polymer product weight (g) ^(d)Determined by GPCin 140° C. o-dichlorobenzene with reference to polystyrene standards: Mn= number average molecular weight, Mw = weight average molecular weight^(e)The molar ratio of AP to E in the copolymer was determined by 1H NMRanalysis. ^(f)Determined by DSC ^(g)[M] = [B] = 0.02 mmol, 50 mL toluene^(h)Syndiotactic polymer of AP

[Example 2] Physical Properties of E-AP Copolymers (P1 to P5)

A film was prepared using each copolymer P1 to P5. The measurementresults of the physical properties of the prepared films are shown inTable 2 and FIGS. 7 and 8 .

The E-AP copolymers P1 to P5 could be processed into a colorless andhighly transparent film with a maximum transparency of 85% in thevisible region by melt pressing (FIG. 7 ). The molecular weight of eachcopolymer significantly affected the mechanical properties (Table 2 andA of FIG. 8 ). The copolymer P1 had a relatively small number averagemolecular weight, exhibited stress softening after 600% elongation at aspeed of 200 mm·min⁻¹, and soft viscoelastic behavior (A of FIG. 8 ). Incontrast, the static stress-strain curves of longer-chain copolymers P2to P5 exhibited typical characteristics of a thermoplastic elastomer(Table 2 and A of FIG. 8 ). The tensile strength increased as themolecular weight increased, and with respect to P5, the tensile strengthof 10.2 MPa and the strain of >2000% were reached. With respect to P2 toP5, the toughness values respectively reached from 31.4 to 68.2 MJm⁻³,which has been conceivably the highest value ever among the polymershaving a self-healing ability at room temperature. The tensile strength,Young's module, and elastic strain recovery of the copolymer increasedwith the molecular weight (Table 2). In the stress-strain test of 1000%elongation, the copolymer P5 gave a residual strain of 6% in the firstcycle and a residual strain of 9% in the tenth cycle to demonstrateexcellent fatigue resistance (B of FIG. 8 ). A sample of the copolymerP5 was subjected to a cycle of elongation of 1000% and release, and thenallowed to rest for 3 hours to obtain a completely recoveredstress-strain curve (C of FIG. 8 ).

TABLE 2 Initial elastic Elongation Stress Tensile Mn modulus at breakrecovery strength Toughness Copolymer (10³ g mol⁻¹) (MPa) (%) (10Cycles; %) (MPa) (MJ/m³) P1 41 3.6 ± 0.1 >3200 — 0.16 ± 0.01 — P2 90 2.8± 0.5 2164 ± 104 52 3.1 ± 0.3 31.4 ± 2.9 P3 173 5.9 ± 0.6 2228 ± 76  784.6 ± 0.6 44.5 ± 8.8 P4 344 9.1 ± 0.7 2205 ± 44  86 6.8 ± 0.5 54.6 ± 6.5P5 552 13.5 ± 0.3  2054 ± 185 91 10.2 ± 0.6  68.2 ± 11 

[Example 3] Copolymerization of APR and Ethylene

A substituted 2-allylanisole was synthesized according to the methoddescribed in the following literature.

(1) P. Anbarasan, H. Neumann, and M. Beller, Chem. Eur. J., 17,4217-4222 (2011).(2) H. Jiang, W. Yang, H. Chen, J. Li, and W. Wu, Chem. Commun., 50,7202-7204 (2014).

A polymerization reaction was performed in the same manner as in Example1 by changing the monomer, the complex, the ratio of the monomer to thecatalyst, the reaction time, etc. as shown in Table 3. The measurementresults of the physical properties of the obtained polymers are shown inTable 3 and FIGS. 9 to 32 .

Using AP^(R) as a monomer, an alternating ethylene—substituted2-allylanisole (E-AP^(R)) copolymer product was obtained. Using 2000equivalents or 5000 equivalents of anisylpropylene, high molecularweight copolymers P6 to P11 were obtained. The copolymers P6 to P11showed a wide range of glass transition temperatures depending onvarious substitution components of the anisyl moiety. It was confirmedthat the yield and the molecular weight were enhanced by increasing theratio of the monomer to complex and the reaction time. Further, it wasrevealed by a ¹³C {¹H} NMR analysis that the copolymers (P6 to P11) hadmainly alternating AP^(R)-E sequences (about 57 to 78%), and someAP^(R)-(E)_(n)—P^(R) sequences (n≥2, about 20 to 43%) andE-AP^(R)-AP^(R)-E sequences (0 to 4%) similarly to P5. In the followingformulas, each copolymer is schematically expressed only by analternating AP^(R)-E sequence, which is the main sequence.

TABLE 3

Activity (kg Run [O]:[M] Time Yield mol- M_(n) ^(d) M_(w)/M_(n) AP^(R)/ET_(g) ^(f) ^(a) [O] ^(b) (h) (g)^(c) Sc⁻¹h⁻¹atm⁻¹) (×10³) ^(d) ^(e) (°C.)  1 AP  500:1  0.5 1.60 171 106 1.9 40/60 6  2 P4 2000:1  6 3.05 51344 1.7 45/55 5  3 P5 5000:1 24 8.35 35 552 2.0 46/54 6  4 AP^(nHex) 500:1^(g)  2.5 2.43 49 164 1.5 36/64 −31  5 P6 2000:1 20 4.33 22 4641.7 42/58 −28  6 AP^(F)  500:1^(g) 10 min 1.88 564 124 1.9 42/58 5  7 P75000:1 10 7.94 79 446 1.8 46/54 4  8 AP^(FF) 1000:1^(g)  4 3.33 42 1251.8 36/64 2  9 2000:1^(h) 15 3.64 24 338 1.8 34/66 0 10 AP^(Me) 500:1^(g)  1.5 1.96 65 105 1.8 42/58 9 11 P8 2000:1  9 3.35 37 420 1.638/62 11 12 AP^(rBu)  500:1^(g)  4.5 1.96 22 150 1.8 42/58 23 13 P92000:1 48 4.11 8 424 1.7 40/60 21 14 AP^(Naph)  500:1^(g)  2 2.00 50 1152.0 41/59 52 15 P10 2000:1 16 3.85 24 259 1.8 41/59 47 16 AP^(Cl) 500:1^(g) 15 min 2.20 44 202 2.1 38/42 18 17 P11 2000:1  1.1 3.89 35424 2.0 39/61 18 ^(a)Condition: [M] (0.01 mmol). [Ph₃C][B(C₆F₅)₄] (B)(0.01 mmol), ethylene (1 atm), 150 mL toluene, 20° C. (unless otherwisespecified) ^(b)Feed ratio (mole) of APR to scandium complex ^(c)Polymerproduct weight (g) ^(d)Determined by GPC in 140° C. o-dichlorobenzenewith reference to polystyrene standards: Mn = number average molecularweight, Mw = weight average molecular weight ^(e)The molar ratio of APRto E in the copolymer was determined by H NMR analysis. ^(f)Determinedby DSC ^(g)[M] = [B] = 0.02 mmol, 50 mL toluene ^(h)[M] = [B] = 0.01mmol, 50 mL toluene

[Example 4] Physical Properties of E-APR Copolymers (P6 to P11)

Films were prepared using copolymers P6 to P11. The measurement resultsof the physical properties of the prepared films are shown in Table 4and FIGS. 33 to 35 .

The films of the copolymers P6 to P11 showed various mechanicalproperties because the range of Tg among the copolymers P6 to P10 wasbroad (A of FIG. 33 ). The n-Hexyl-substituted copolymer P6 was a stresssoftening material and was able to stretch up to 10000% withoutbreaking. A fluoro-substituted copolymer P7 and a methyl-substitutedcopolymer P8 are typical elastomers. P7 and P8 showed significantlyhigher initial elastic modulus and tensile strength compared to P1 to P5(Table 2, 4, A of FIG. 33 ). The elongation at break of P7 or P8 islower than P5 (Table 4), but these two elastomers have a toughnesshigher than P5 to demonstrate that P7 and P8 are endowed with bothrigidity and toughness. In contrast, the t-butyl-substituted copolymerP9 is a flexible plastic, which showed ductility and strain hardeningwhen it was drawn at room temperature and a tension rate of 200 mmmin⁻¹(Table 4). The naphthyl copolymer P10 is a rigid plastic at roomtemperature. P10 showed a remarkable reduction in strain at break (7 to9%), a high tensile stress (50 MPa or more), and an extraordinary highinitial elastic modulus (1000 MPa or more). This is because it isvitrified at room temperature (Tg=49 to 53° C.). The chloro-substitutedcopolymer P11 (Tg=18° C.) was a flexible plastic, and showed a highinitial elastic modulus (218 MPa or more), a medium elongation at break(954%), a high tensile strength (22.7 MPa), and a toughness of 117MJm⁻³.

E-AP(APR) copolymers showed excellent self-healing characteristics inaddition to excellent elasticity (FIG. 34 ). When the damaged surfacesof P2 film sample were jointed together at room temperature, the twodamaged parts were rapidly healed (A of FIG. 34 ). After only 5 min, thehealed sample could be stretched up to 1000% (50% of the original value)(B of FIG. 34 , ii). As the healing time became longer, the healedcondition became better. After 120 hours, the damaged parts werecompletely healed (B of FIG. 34 , v). This is verified by causing afracture at another site (a site different from the healed site), andadditionally observing an elongation corresponding to the elongation ofthe sample at the initial stage. The stress-strain curve of the healedsample nearly overlapped the stress-strain curve of the material at theinitial stage. In most cases, only the difference was elongation atbreak (B and C of FIG. 34 ). P5 that is a polymer having a highermolecular weight required a longer healing time, and recovered to 90% ofthe original elongation after 120 hours at room temperature (C of FIG.34 ). The healed sample of P5 showed a tensile strength as high as 6.7MPa at an elongation of 1520% (C of FIG. 34 , v).

A film of P5 was cut with a razor blade to make a nick and then leftstanding in air at 25° C. After 5 min, a damage was visually notrecognizable (see D of FIG. 34 ). Amazingly, this rapid self-healingoccurred also in water (see E of FIG. 34 ). The film of P2, which wascompletely cut in advance and healed in water at 25° C. for 96 hours,could be elongated up to 1670% (about 80% of the original value) (F ofFIG. 34 , iv). In a case in which a P2 sample was cut and healed inwater at 37° C. (human body temperature) for 24 hours, complete healingwas observed (G of FIG. 34 , iv). Further, for this damaged sample,self-healing was possible even in an acidic solution or a basic solution(1 M HCl, 1 M NaOH, etc.) (H of FIG. 34 ). The aforedescribedcharacteristic are extremely contrastive to the existing self-healingmaterials based on ionic aggregation or hydrogen bonds, which hardlyfunctioned in water under an acidic condition, or a basic condition (NonPatent Literature. 2).

Since P6, which was a stress softening material, and had highadhesiveness, it exhibited high speed self-healing characteristics (I ofFIG. 34 ). Amazingly the fluoro-substituted copolymer P7 and themethyl-substituted copolymer P8 exhibited better healing efficiency atroom temperature than P5 (J and K of FIG. 34 ). When the healing timewas 5 days, the recovery rates of elongation at break were 86% and 87%respectively. Further amazingly, the P7 and P8 samples after re-repairshowed tensile stresses of 11.9 MPa and 12.6 MPa respectively. Thesevalues are the highest among those ever reported for autonomous healingmaterials, and higher than any existing self-healing materials in theinitial stage (Non Patent Literature 2).

The t-butyl-substituted copolymer P9 was a flexible plastic at roomtemperature, and the naphthyl copolymer P10 was a rigid plastic at roomtemperature, but both of them exhibited excellent elastic properties athigh temperature (data not shown). Owing to thermally peculiarplasticity and elasticity, there is flexibility in a shaping operation.As shown in FIG. 35 , the film sample of P10 having a predeterminedshape was stretched to take a deformed shape, when an external force wasapplied at 80° C. When the sample was cooled to room temperature, thedeformed shape was fixed. When the sample was heated again to 80° C.without applying any external force, it was observed that the theoriginal shape was almost completely restored. Further, as shown in FIG.39 , the film sample of P9 was stretched to take a deformed shape, whenan external force was applied at 50° C. When the sample was cooled to20° C., the deformed shape was fixed. When this sample was placed inwater at 50° C. to be heated without applying any external force, it wasobserved that the the original shape was almost completely restoredwithin 5 sec.

Further, the results of separate measurements of two shape-memory cyclesat a temperature of 50° C. (thermo-mechanical analysis (TMA)) for a P9film sample are shown in FIG. 40 . As obvious from the graph shown inFIG. 40 , the film sample of P9 functioned as a shape-memory material bycontrolling the temperature, and the shape fixed rate and the shaperecovery rate were excellently as high as 99%. Such a thermo-responsivematerial having a controllable shape changing behavior is also a highlydesirable material in the real world device application.

TABLE 4 Self- healing Before use efficiency Initial and After recoveryelastic Tensile Elongation Required Tensile Elongation M_(n) modulusstrength at break Toughness time strength at break Toughness Copolymer(10³ g mol⁻³) (MPa) (MPa) (%) (MJ/m³) (h)^(a) (MPa) (%) (MJ/m³) AP-alt-EP2 90  2.8 ± 0.5  3.1 ± 0.3  2164 ± 104 31.4 ± 2.9 48 2.5 2005 26.8(96%) P5 552 13.5 ± 0.3 10.2 ± 0.6  2054 ± 185  68.2 ± 11.0 120 6.7 152034.6 (90%) AP^(F)-alt-E 124  9.2 ± 1.2  5.8 ± 0.5 1806 ± 84 40.2 ± 4.5 54.4 1788 32.6 (93%) P7 446 28.5 ± 2.8 16.6 ± 0.6 1454 ± 47 72.4 ± 6.5120 11.9 1303 47.2 (86%) AP^(FF)-alt-E 125  9.7 ± 0.2  7.4 ± 0.6 1778 ±59 40.9 ± 2.5 5 6.1 1786 38.7 (99%) 338 10.2 ± 0.1 11.7 ± 0.7 1385 ± 2146.9 ± 3.4 AP^(Me)-alt-E 105  86.2 ± 16.1 13.0 ± 0.2 1236 ± 49 71.4 ±2.7 120 7.2 864 31.0 (70%) P8 420 139.6 ± 25.5 17.7 ± 0.3 1272 ± 52 84.8± 4.8 120 12.6 1117 49.7 (87%) AP

-alt-E 150 648.3 ± 36.8 29.7 ± 3.1  34 ± 12  5.3 ± 1.9 — — — — P9 424467.9 ± 22.9 15.6 ± 0.8 565 ± 5 66.1 ± 2.2 Ap

-alt-E 115 1013.2 ± 82.1  51.8 ± 1.5  9 ± 1  2.5 ± 0.4 — — — — P10 2591221.6 ± 54.5  52.1 ± 0.3  7 ± 1  1.9 ± 0.3 AP

-alt-E 164 1.4 <0.1 >10000 0.68 5 min <0.1 >10000 0.59 (100%) P6 464 4.3<0.1 >10000 1.71 1 <0.1 >10000 1.71 (100%) AP

-alt-E P11 424 218 ± 34 21.7 ± 0.9  954 ± 51  117 ± 8.6 — — — — ^(a)Theself-healing efficiency was calculated based on the recovery rate of theelongation at break after recovery with respect to the elongation atbreak before use.

indicates data missing or illegible when filed

As one of the reasons why the copolymer produced in Example aboveexhibits elastomeric properties, self-healing ability, and shape-memorycharacteristics, conceivably construction of a network, in which thealternating unit of anisylpropylene and ethylene acts as a soft moiety,and the hard crystalline unit of ethylene-ethylene chains acts as aphysical crosslinking point, is a key issue. In the case of theconventional self-healing materials, which utilize hydrogen bonds, ionicbonds, or the like, such interaction is weakened in water and mayfunction only poorly (Non Patent Literature 2). However, in the E-AP(APR) copolymer in Examples above, the crystalline unit ofethylene-ethylene chains, and the alternating unit of anisylpropyleneand ethylene are not affected by water. Therefore, there is a bigadvantage that it can exhibit the self-healing ability and shape-memorycharacteristics not only in the atmosphere, but also in water, or anacid, or alkaline aqueous solution. Two E-AP copolymers with a reduced“alternating property” respectively having an AP content of 25 mol %(P2′), and 12.5 mol % (P2″) were synthesized. The healing efficiency ofthe copolymer P2′ was significantly lower than that of P2, and P2″ hadcompletely lost its healing ability (it is however useful as atransparent film or the like for other applications, such as anintermediate layer film to be disposed between a polar film and anonpolar film).

With respect to the film molded product of P5 (thickness 1 mm) preparedabove, wide-angle X-ray diffraction (WAXD) analyses were performed underdifferent temperature conditions (25° C., 60° C., 90° C., 120° C., and150° C.). The results are shown in FIG. 37 . As shown in FIG. 37 , anX-ray diffraction peak attributed to the (110) plane of an orthorhombiccrystal was observed at 15.26 nm⁻¹. This is considered to be derivedfrom a crystalline nanodomain formed by aggregation of ethylenehomo-polymerization sequences contained in the film. This diffractionpeak was not observed under the condition of 150° C. This suggests thatthe crystalline nanodomain melted to lose the crystallinity.

Also, with respect to the film molded product of P5 (thickness 1 mm), asmall-angle X-ray scattering (SAXS) analysis was performed at roomtemperature (25° C.). The results are shown in FIG. 38 . As shown inFIG. 38 , a broad scattering peak having the peak top at about 0.283nm⁻′ was observed. This scattering peak is considered to be derived fromthe crystalline nanodomain. The average domain size was calculatedaccording to the equation d=2it/q to find 22 nm.

The analyses of WAXD and SAXS were performed with the BLO5XU beamline ofa SPring-8 (Japan Synchrotron Radiation Research Institute, Hyogo,Japan). The X-ray wavelength was set at 0.1 nm. The 2D WAXD and 2D SAXSpatterns were recorded using a PILATUS 1M (DECRIS, Switzerland) with941×1043 pixels having a pixel size of 172×172 μm² as the X-raydetector. The distance from the sample to the detector was 106 mm forWAXD and 3906 mm for SAXS. The analysis was performed under precisetemperature control using a sample chamber equipped with a block heater.The scattering vector is defined as q=(4π/λ)·sinθ(2θ is the scatteringangle). The scattering vector was calibrated using the peak position ofCeO₂ for WAXD, and collagen for SAXS. TGA was recorded with EXSTARTG/DTA6200 Thermal Analyzer (Hitachi High-Tech Science Corporation,Tokyo, Japan). The rate of temperature increase was set at 10° C. min⁻¹.

An ultrathin film was formed by evaporating a solvent of a CH2C₁₂solution of P5 (0.5 mg/mL) on a 400-mesh carbon coated copper grid, andused as a TEM analysis sample. The TEM analysis was performed using amodel JEM-2100F/SP of JEOL operated at an accelerating voltage of 200kV. A phase separated structure was observed in which there werenanoscale crystalline domains dispersed in a continuous matrix (FIG.36A).

The P5 film produced in the same manner as above was processed into abag form. A string was passed near the opening of the bag to hang it,and water was poured up to half the height. A sewing needle was stuckfrom the bottom of the bag (bottom filled with water) upward (toward theopening), and after confirming that the needle had entered the waterfilling the bag, the needle was pulled out backward from the bag. Thisoperation was carried out within about 3 sec. Although the needle waspulled out completely, the pinhole pierced by the needle at the bagbottom disappeared immediately by heeling, and leakage of water from thebag did not happen at all. From this it can be understood that themolded product of the present invention exhibits a self-healing abilityeven when it is used as a member to be placed at the interface between aliquid and a gas. From the above results, it can be understood that themolded product of the present invention can be utilized, for example, asa member for closing the wells of a microplate in which a plurality ofwells are provided, and through the use of the molded product of thepresent invention, a sample (including a liquid sample) can be injectedinto, or taken out from the well inside even in a hermetically sealedstate.

The P5 polymer was processed with a vacuum hot press and formed into asquare platy shape with a length and a width of 2 cm and a thickness of5 mm. This molded product sample was completely cut with a cutter at theposition about 1 cm-long from the edge (midpoint) (into two pieceshaving the original thickness and length, and the width of half thelength). When the cut surfaces of the two pieces were pressed togetherby hand at room temperature, they were jointed to one piece. The upperpart and the lower part of this jointed sample were held with clipsrespectively. The upper clip was fixed to hang the sample such that thejointed surface is oriented approx. parallel to the floor. A 1.2 kgweight was hung on the lower clip and observed for about 1 min. Thejointed molded product did not separate and maintained the integrity.

A solution of the P5 polymer dissolved in toluene is applied to a metalsurface and dried to remove toluene. A film is formed on the metalsurface. When a nick is formed in the surface of this film with acutter, it will self-heal and close the nick to form a uniform film asin the case of a shaped film.

According to the present invention, it is possible to yield a moldedproduct to which one or more functions such as high transparency, highelasticity, self-healing characteristics, and shape-memorycharacteristics has been imparted, by controlling the molecular weightof a polar olefin-based polymer to be used as a raw material, themonomer type, the polymerization ratio in the case of a copolymer, orthe like. According to the present invention, it is possible to providea molded product that is useful for various future application fields(such as a self-healable implant for a human body).

INDUSTRIAL APPLICABILITY

An olefin-based molded product of the present invention is applicableto, but not limited to, uses such as materials, surface coatingmaterials, equipment, parts, and products for various industries (forexample, medical care, construction, transportation, andelectronic/electric industries). In particular, it is more favorablyutilizable in the fields, where detection of a damage is very difficult,or repair needs high cost, or even not possible, for example, forequipment on the seabed, equipment or medical materials in outer space,instruments, etc.

1. An olefin-based molded product comprising a copolymer comprising astructural unit of at least one polar olefin monomer (A) and astructural unit of at least one nonpolar olefin monomer (B), thecopolymer comprises as a main sequence, alternating (A)—(B) sequence inwhich the structural units of (A) and (B) are aligned alternatingly, and—(B)—(B)— sequence which is the polymerization sequence of (B), wherestructural units of two or more kinds of nonpolar olefin monomers areincluded, a random copolymer, an alternating copolymer, a blockcopolymer, or another ordered copolymer constituted with structuralunits of two or more kinds of nonpolar olefin monomers is also includedas the —(B)—(B)— sequence,
 2. The olefin-based molded product accordingto claim 1, wherein the proportion of the alternating (A)—(B) sequencein the total sequences of the copolymer is 40 mol % or more, and whereinthe proportion of the —(B)—(B)— sequence in the total sequences of thecopolymer is 60 mol % or less.
 3. The olefin-based molded productaccording to claim 1, the olefin-based molded product has crystallinenanodomain derived from the —(B)—(B)— sequence.
 4. The olefin-basedmolded product according to claim 1, wherein the proportion of the polarolefin structural unit in the total structural units in the polymer is20 mol % or more.
 5. The olefin-based molded product according to claim1, wherein the number average molecular weight of the polymer is 2.0×10³or more.
 6. The olefin-based molded product according to claim 1, whichis used as a self-healing material, or which is used as a shape-memorymaterial.
 7. The olefin-based molded product according to claim 7,wherein a self-healing rate of the olefin-based molded product is 80% ormore within 5 days.
 8. The olefin-based molded product according toclaim 7, wherein a shape fixed rate and a shape recovery rate of theolefin-based molded product is 80% or more.